DE2601278A1 - CYCLIC PENTAERYTHRITE DIPHOSPHATE AND DIPHOSPHORAMITE DATE - Google Patents

Description

DR. BERG DiPL.ING. STAPF

DIPL.-ING. SCHWABE DR. DR. SANDMAIR O β Π 1 2 7 8 PATENTANWÄLTE

8 MUNICH 86, POST BOX 86 02 45

_6th

Be / Ro ^{Ί b JMlJ}

Michigan Chemical Corporation Chicago, Illinois 60606 / USA

"Cyclic pentaerythritol diphosphates and diphosphorus

amidate "

This application is a continuation-in-part of application Serial Ho. 429.607 dated 2.1.1974.

The compounds of the present invention can be used as' MCC-1091 -2-

+49 89 98 8272 8 Munich 80, Mauerkircherstraße 45 Banks: Bayerische Vereinsbank Munich 453100

987043 Telegrams: BERGSTAPFPATENT Munich Hypo-Bank Munich 3892623

983310 TELEX: 0524560 BERG d Postscheck Munich 65343-808

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cyclic pentaerythritol diphosphates and diphosphoramidates be marked. The diphosphates are also characterized by halogen substitution on the oxyali— phatic or oxyalicyclic groups of the ester part. The diphosphoramidates can optionally contain halogen atoms on the hydrocarbon substituents attached to the nitrogen atoms.

During the last few years a large number of developed fire retardants that are used on an almost equal number of flammable materials should be. Cellulosic materials such as paper and wood and polymeric materials such as synthetic fibers and larger, for example puffed plastic objects, are just two examples of materials for which fire retardants were developed. It has long been known to those skilled in the art that for each class of inflammatory Materials such as those used for high molecular weight synthetic polymers, some fire retardant Additives in some polymers are more effective than in others. In fact, many fire retardant additives are which are highly effective in some polymeric systems, practically ineffective in other polymeric systems. It is therefore so that most fire retardants containing halogen and phosphorus atoms do not ensure that any given halogenated or phosphorus containing

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Compound useful fire retardant properties all or even any polymeric systems. Continue to have professionals in addition to improvement the fire retardancy of many polymeric materials at the same time required that the required fire retardancy with a minimal effect on the other properties of the Polymers must take place, such as their light stability, processability, their flexural, tensile and impact strength. When weighing all of the previous considerations and there Developing polymeric formulations with good fire retardancy as well as with satisfactory balance of the others Properties, accordingly results in a task that has been continuously used in the past and at present requires a high degree of inventive development.

Form compounds that can impart useful fire retardant properties to synthetic polymeric systems the main subject of this invention »

Further items can be found in the description below.

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4ο

The compounds of the present invention have the general formula

• tr TD ^ Π Τ> "V

wherein the radicals X and X, independently of one another, oxygen or sulfur atoms, and Y and Y ₁ , independently of one another, monovalent halogenated oxyaliphatic or oxyalicyclic radicals or a radical

—ST

R ₁

are, in which the radicals R and R ₁ , independently of one another, are a hydrogen atom, a monovalent hydrocarbon or a monovalent halogenated hydrocarbon.

The compounds of the above general formula include both the diphosphate esters and the diphosphoramidates of pentaerythritol. The compounds can also be generic as 3,9-substituted-2,4 »8,10-tetraoxa-3,9-diphosphaspiro- / 5" .57-undecane-3,9-dioxides or disulfides.

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As indicated in the general formula above, the XG groups attached to the phosphorus atoms can be either sulfur or oxygen atoms. Oxygen is the preferred substituent for most compounds provided herein, but the presence of thiophosphoryl, d "h _o

in some cases may be beneficial because of the difference in properties by their presence instead caused by the more common phosphoryl groups »

The Y groups can be monovalent halogenated oxyaliphatic ones or oxyalicyclic groups or amino groups of the formula

- Ή

be, in which the R or IL groups are hydrogen atoms, are monovalent hydrocarbon or halogenated monovalent hydrocarbon radicals.

The oxyaliphatic or oxyalicyclic groups can be alkoxy, olefinic-oxy and cycloalkoxy groups with each Number of carbon atoms, preferably no more than about 12, and in particular no more than about 6 carbon

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41.

be atoms of matter. The halogen atoms present in the oxyaliphatic and oxyalicyclic groups include fluorine, chlorine, bromine and iodine atoms. Of the foregoing, chlorine and bromine are preferred. The number of halogen substituents is limited only by the number of sites on the aliphatic or alicyclic group available for their substitution. As a practical matter, the number of halogen atoms attached to the aliphatic or alicyclic groups having six or fewer carbon atoms should usually be from about one to about six. Examples of suitable halogenated monovalent oxyaliphatic or oxyalicyclic G groups include bromoethoxy-j dibromoethoxy-, dibromopropoxy-j dibromobutadienoxy-} tribromobutoxy-> dichlorocyclohexoxy-, dichlorobromocyclohexoxy _{, bromo-dibromopropoxy-iodo-chlorohexoxy-7-} bromo-dibromopropoxy-iodo-chlorohexoxy-7oxy-chlorohexoxy-iodo-chlorohexoxy-7-chlorohexoxy-iodo-chlorohexoxy-7-chlorohexoxy-iodo-chlorohexoxy-chlorodoxy-chlorohexoxy-iodo-chlorohexoxy-7-bromoprohexoxy-iodo-chloro-chlorohexoxy-iodo-chlorohexoxy-7-chloro-chlorohexoxy-iodo-chlorohexoxy-iodo-chlorohexoxy-iodo-chloro-chlorohexoxy-iodo-chlorohexoxy-iodo-chloro-chlorohexoxy Chlorpentabromcyclohexoxy-, Fluorhexabrombutoxy- "Tetrafluorcyclobutoxy-, Dijodbutenoxy-> Difluorallyloxy _T Dibromdichlorhexenoxygruppen and the like.

If the Y-G groups are oxyaliphatic G groups, it is preferred that each of these groups is a remainder

C ——

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is, in which the radicals Z ₁ and Zp, independently of one another, are fluorine, chlorine, bromine, iodine and / or hydrogen atoms and Z, a fluorine, chlorine, bromine and / or iodine atom is β Examples of suitable Groups of the abovementioned JTe opentyl oxy structure are given in Table I below. Table I is used for illustration purposes only, without limiting the scope of the invention. The following is a partial list of preferred compounds which have the above-mentioned heopentyloxy part: 3,9-bis (2,2- / Mbromomethyl7-3-bromopropoxy) -2.4 _} 8.10-1 et raoxa-3,9-diphosphaspiro / 5., 57-undecane-3 »9-dioxide, 3,9-dis (2,2- ^ dichloromethyl7_3_chlorpropoxy) -2,4,8,10-tetraoxa-3,9-dipho sphaspiro / 5. ^ 7- undecane-3,9-dioxide, 3,9-bis (2,2 - / ^ dimethyl7-3-chloropropoxy) -2,4,8,10-tetraoxa-3,9-dipho sphaspiro / 5 x 5 / - undecane -3,9-dioxide, 3,9-bis (2, 2- ^ imethy] J7-3-bromopropoxy) 2,4,8,1O-tetraoxa-3,9-diphosphaspiro / 5.57 ~ undecane-3,9- dioxide and 3,9-bis (2,2 - / ^ ibromomethyl7-3-chloropropoxy) -2,4, 8,1O-tetraoxa-3,9-diphosphaspiro / 5 ^ 7-undecane-3,9-dioxide.

Table I. ^Z 2 ^Z 3 group ISl Br Br 1 Br Cl Cl 2 Cl H Cl 3 H H Br 4th H Cl Br LTv Br

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- sr -

The Y groups can also be amino groups of the formula

be, in which the radicals R and R * hydrogen atoms, monovalent Hydrocarbon or halogenated monovalent hydrocarbon radicals are.

The monovalent hydrocarbon groups can be aliphatic, naphthenic or aromatic and can be of any size but preferably no more than about 12 carbon atoms and especially no more than about 6 carbon atoms. Suitable preferred monovalent hydrocarbon groups include phenyl and alkyl groups with up to about 6 carbon atoms. The halogen atoms can be fluorine, chlorine, bromine or iodine and are preferred Chlorine or bromine. The number of people attached to the R groups Any halogen atoms present are only limited by the positions on the R-G groups available for substitution. Preferably, each of the R groups can usually have a maximum of about 6 halogen atoms per R group and in particular contain a maximum of about 3 halogen atoms per R group.

The monovalent hydrocarbon groups are preferably aliphatic ^, halogenated aliphatic, aromatic or

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- ar-

halogenated aromatic groups containing no more than about 12 carbon atoms, the halogenated Groups have up to about 6 halogen substituents per group.

Examples of suitable amino groups include amino, diethylamino, diphenylamine, propylamine, methylamine, Dimethylamine, N-phenyl, N-methylamino, phenylamino, p-Tolylamino-, bromophenylamino-, chloromethylamino-, di- (chloroethyl) -amino-, N-ethyl, N-tribromocyclohexylamino, Di- (tribromochloroethyl) -amino-, di- (dichlorobromoisopropyl) -amino-, Butadienylamino, di (fluorocyclopentyl) amino and di (diiodoethyl) amino groups.

All previously named and mentioned Y and Y groups, which can be linked to the diphosphoryl or dithiophosphorylpentaerythritol group can also be used as 3,9-substituted ea-2,4,8,1 O-tetraoxa-3,9-diphosphaspiro- / 5.57-undecane-3,9-dioxide or disulfide. The numerical labels used to identify the Compounds of this invention can be used by referring to the general formula below in which the members of the heterocyclic rings are numbered.

_χ 10 11 1 2 χ ■

G CH _2n ^ ^ CH ₂ O ^

■ "C

0 —— CH ^ "^ CH xj 8 - 7 ² 5 ² 4

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Two typical compounds are 3,9-bis (2,3-dibromopropoxy) -2,4,8,1O-tetraoxa-3,9-diphosphaspiro / 5.57-undecane-3,9-dioxide and 3,9-bisUT, N-diethylamino) -2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5. ^ 7-undecane-3,9-dioxide. Two other typical compounds are the 3 »9 disulfide analogs of above two connections. Additional 3> 9-bis-substituted compounds formed by the halogenated oxyaliphatic and oxyalicyclic mentioned above Groups and optionally halogenated substituted amino groups on the diphosphoryl and dithiophosphoryl pentaerythritol groups attaches form further examples of compounds within the scope of this invention. The disulfide analogs of the foregoing compounds are further examples.

In addition to the 3,9-bis-substituted compounds, there are another large number of 3,9-substituted compounds, wherein the 3- and 9-substituents are different from each other, also within the scope of this invention. The substituents can change with formation of mixed ones Diphosphate esters, mixed diphosphoramidates, and combinations of phosphate and phosphoramidate compounds. Combination examples of 3- and 9-substituents include Dibromoethoxy and tribromochlorobutoxy, dibromopropoxy and dibromochlorneopentyloxy, diethylamino and phenylamino, diphenylamine and tribromoethylamino, dibromophenyl

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- Vr -

amino and dibromopropoxy, bromoethylamino and dibromochlorobutoxy, Diethylamino and dibromopropoxy and unsubstituted Imino and diiodoisopropoxy groups.

The compounds of the present invention can thereby be prepared that a 3,9-dihalo-2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5. ^ / - undecane-3,9-dioxide or disulfide with an alcohol or an amine to form the appropriate diphosphate ester or diphosphoramidate. The reaction proceeds according to the equation:

JL JL-i JL JL- *

HaI-P C _x P-HaI + YH -> YP Ov PY

^ 0-CHo CH ₀ -O ^ ^N O-CH <CH ₀ -O '

^l 2

2 ^{w ±} 2

wherein Y has the meaning given above and Hai Indicates halogen atom.

The metal salts of alcohol or amine can be used as further reactants instead of alcohol or amine will. If one wishes the two Y-G groups to be different from one another, two different ones should be used Y-H reactants can be used. The reaction can be carried out by simply adding the halophosphate and mixing the alcohol or amine reactants together and the mixture under mild conditions heated long enough. The reaction conditions are

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At

vary widely depending on the reactants, however, heating the reactants under moderate reflux conditions for up to three or four hours is useful in preparing many of the compounds of this invention. Catalytic amounts of a metal salt or oxide, such as magnesium chloride, calcium oxide, calcium chloride, titanium chloride and vanadium acetate, or stoichiometric amounts a weak organic base such as pyridine or triethylamine can be used to complete the termination to speed up the response. The halophosphate starting material can be prepared by reacting pentaerythritol with phosphorus oxyhalide. Chlorophosphate is a preferred reactant and phosphorus oxychloride is therefore a preferred precursor of this reaction partner.

Also included in the scope of this invention are pentaerythritol cyclic diphosphoramidates, wherein the Y groups are amino groups of the formula

are, in which the radicals R and R _{1 are} hydrogen atoms, monovalent hydrocarbon or halogenated monovalent hydrocarbon groups, but with the proviso that when the radicals R and R ^ are both hydrogen and the radicals X and X.

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- wr-

are both oxygen, Ύ must be different _{from Y 1.} The monovalent hydrocarbon groups are preferably aliphatic, halogenated aliphatic, aromatic or halogenated aromatic groups containing no more than about 12 carbon atoms and preferably no more than about 6 carbon atoms, the halogenated groups having up to about 6 halogen substituents per group and preferably up to about three halogen substituents per group. The halogen atoms can be fluorine, chlorine, bromine or iodine atoms and are preferably chlorine or bromine atoms. It is further preferred that when the Y groups are amino groups, these Y groups have the formula

/ ^E

have, wherein R has the meaning defined above.

The compounds of the present invention are useful as fire retardants in polymeric formulations. Certain compounds also exhibit pesticidal properties, which are suitable for use in agriculture as well as for pest control in houses.

The following examples serve for further explanation without restricting the scope of the invention. So far

-U-

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Unless otherwise stated, all temperatures are in degrees C, all weights in grams and all volumes in ml - *

example 1

29.7 g of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5 are mixed. _- 5-7-undecane-3,9-dioxide, 43.6 g of 2,3-dibromopropanol and 0.1 g of magnesium oxide together and heated to 110 ° while driving off the hydrogen chloride formed. The formation of hydrogen chloride will cease after about 2 hours, after which the reaction mixture is allowed to cool to room temperature. The viscous product obtained is washed with ammonium hydroxide at 6O ⁰ C and then with water. The slightly brown viscous liquid is dried under vacuum. The calculated bromine content for 3.9- = §is (2,3-dibromopropoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5, 57-undecane-3,9-dioxide is 48, 5 fo. A bromine content of $ 47.7 is determined by means of elemental analysis »

Example 2

Dibromopentaerythritol-cyclic-chlorophosphite is produced

PCI

BrCH ₂

BrCH ₂ 'CH ₂ O

by reacting dibromopentaerythritol with a slight molar excess of phosphorus trichloride.

-15-

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The chlorophosphite given above, 380 g, is then reacted with a slight molar excess of gaseous chlorine, 95 g, in the presence of 200 ml of methylene dichloride. Keep 3O ⁰ C - During the chlorine addition an ice bath to the reaction temperature to 25 is used. When the addition of chlorine is complete, the methylene dichloride is evaporated, giving the product 2,2-di- (bromomethyl) -3 ~ chloropropyl dichlorophosphate

CH ₀ Br 0

I t - ^C1

ClCH ₂ C CH _n O - P

- ζ χ

CH ₂ Br

remains behind.

279 g (0.7 mol) of the dichlorophosphate indicated above are mixed with 47.7 g (0.35 mol) of pentaerythritol in the presence of 300 ml of toluene and 0.5 g of magnesium oxide, heated reflux the reaction mixture to add hydrogen chloride to remove. After about 12 hours of reflux, the mixture is allowed to cool and subjected to a vacuum, to remove more hydrogen chloride. Filter remove the white precipitate and wash once with ammonium hydroxide and twice with water and then crystallize from methanol. The product is identified as 3,9-bis (2,2-di-bromomethyl-3-chloropropoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5.57-undecane-3> 9-dioxide j melting point

212 ⁰ C. Calculated halogen content Br 40.7 #, Cl 8.93 #f

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found Br 41.1 1 », Cl 9.12 #.

Example 3

To a suspension of 29.7 g (0.1 mol) 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5 · 57-undecane-3,9-dioxide in 250 ml Benzene is added to 30 g of diethylamino in 50 ml of benzene. The mixture is refluxed for 3 hours and then filtered to remove the precipitated amine hydrochloride. After evaporation of the benzene "remains a clear oil, which crystallizes out after cooling and which is then recrystallized from water. Melting point of the white crystalline product 189.5 to 19O.5 ° C. Calculated for 3.9-Ms (IT, N- Diethylamino) -2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5.57-undecane-3,9-dioxide 42.2 $ C, 7.6 JL H, 7.6 io Kj found 41.1 ° / o C, $ 7.5 H, 7.2 & Ή.

Example 4

146 g of p-bromoaniline and 82 g of triethylamine are added to 122 g of chlorophosphate from Example 3 in 800 ml of toluene. The mixture is heated to 95 ° C. for 4 hours and then allowed to cool. Two layers are formed and the toluene is decanted. The product layer is washed with 800 ml of water and then with boiling acetone and a white solid is obtained; Melting point 276 - 278 ⁰ C. Calculated bromine content was for 3,9-bis- (Np-bromophenyl) amino-2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5:57-undecane-3,9-dioxide 28.2 #j ge

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Found bromine content $ 30.0.

Example 5

Production of 3,9-bis (2,2- ^ imethyl7-3-chloropropoxy) -2,4,8,10-t etraoxa-3,9-diphosphaspiro / 5., 57-undeoane-3,9-dioxide.

748.2 g (3 mol) of 2,2-dimethyl-3-chloropropyl dichlorophosphate are dissolved in 800 ml of toluene. To this are added 209 g (1> 5 mol) of pentaerythritol and 3 g of magnesium oxide. The solution is kept for 9 hours at 11O ⁰ C to reflux, the mixture was filtered and obtains a white solid. This material is washed with 1 l of acetone, then with aqueous ammonia solution, Ρττ about 8 to about 9. This solution is filtered and washed with 2 l of water, then washed with acetone (1 l). The material is dried in an air oven at 105 ° C. for 3/2 hours. 442 g of material are obtained, yield about 63 #}, melting point 282-285 ° C.

Example 6

Manufacture of 3,9-bis (2,2- / dibromomethyl / -3-bromprοροχ $ - 2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5.57-undecane-3,9-dioxido

Heat phosphoryl chloride (50 g) and 0.4 g magnesium oxide to 85 ° 0. Tribromoneopentyl alcohol (300 g, 0.924 mol) is added in portions over 1.25 hours. One sets

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the "reaction continued at 85 ⁰ C for 6 hours. Excess Phosphorylclilorid is distilled off with aspirator vacuum at a pot temperature of 13O ⁰ C. Cool the reaction mixture to 100 ⁰ C., and 0.462 mol (62.8 g) of pentaerythritol and 300 ml of toluene Add more toluene as required The system is refluxed for 6 1/2 hours, cooled to room temperature, filtered and dried at 100 ° C. in an air oven.

The residue is washed with about 1 liter of water. An aqueous ammonia solution is added to give a pg value of about 8. The residue is washed with water and then with acetone and dried finally at 100 ⁰ C in an air oven. Yield: 335 g (83 $>) \ Melting point: 225 - 228 ^C

Example T

Preparation of 3 »9-bis (2,2- ^ chloromethyl7-3-chloropropoxy) -2,4 f 8 »10-tet raoxa-3,9-diphosphaspiro / 5 ..57-undecane-3,9-dioxide.

About 1 mole of 2,2-dichloromethyl-3-chloropropyl dichlorophosphate is added into a 3 liter flask. To this are added 1 g of magnesium oxide, 2 liters of toluene and 0.5 mol of pentaerythritol, The reaction mixture is stirred and refluxed until the acid number is less than 10. The toluene is stripped off and puts the solid part in an oven and dries without it

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to wash. The product is brought, after which it was added 4 hours, "at 11O ⁰ O dried, for grinding and washed with a 5O / 5O acetone / water solution of the product obtained has a melting point of 197 -. 20O ⁰ C and the melt remains clear until Decay at 270 - 280 ⁰ C.

Example 8

The following connections were made:

CH ₃ CH ₂ CH ₂ OP X P-OCH ₂ CH ₂ CH ₅ , (hereinafter referred to as

^ O f ^ --0

Connection "A" designated),

0 0

ClCH ₂ CH ₂ CH ₂ O-PNf P-OCH ₂ CH ₂ CH ₂ Cl, (hereinafter

0 /  \ (T

referred to as compound "B"),

CH, 0 0 CH ^

ι t / «\ / \ t l

BrCH, -CH-OP yC PO-CH-CH ₁₃ Br, (hereinafter referred to as

Nj-ZN-o '

Connection "C" designated),

0 0

BrCH ₂ CHBrCH ₂ OP X P-OCHgCHBrCHgBr, (hereinafter referred to as compound "D"), and

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2801278

CH ₂ Br OO CH ₂ Br

ClCH ₀ -C-CH ₀ OP> C P-OCH ₀ -C-CH ₀ Cl, (hereinafter

CH ₂ Br CH ₂ Br

referred to as compound "E" ").

The compound D given above was prepared according to Example 1 and the compound E according to Example 2. The connections A, B and C were determined according to that in Example 3 of US Pat. No. 3,090,799 (hereinafter referred to as Wahl i.a.), the compounds being identified by means of nuclear magnetic resonance spectroscopy and it was found that by means of this procedure a Obtains purity greater than 95 ^.

The compounds A, B, C and D are typical outside the invention, but within the scope of the invention of Wahl et al. lying connections. Compound E is typical of the pentaerythritol cyclic diphosphates of the presently claimed Invention.

Example 9

The hydrolytic stability of the compounds of Example 8 prepared above was determined by the following procedure determined: A magnetically stirred emulsion containing 4 g of compounds A, B, C, D or E, 1 g of Emcol Am2-10C emulsifying agent (Emcol AM2-IOC emulsifier is a mixture

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ι.

from phosphated non-ionic plus non-ionic free acid, a trademark of Witco Chemical Corporation, NeW York, ΪΓ.Υ.) and 45 g of water

one at 100 ⁰ C for 44 hours. The acid number of the emulsion is then determined by titration with a standard potassium hydroxide solution, the results being given in Table II below.

Table II

Hydrolytic stability studies

Compound acid ^ compound / E χ 100? ^ ' (M g K0H / g sample)

A. 21.6 911 B. 19.3 814 C. 23.4 987 D. 9.45 399 E. 2.37 —__

'Percentage decrease in the hydrolytic stability of compounds according to the prior art compared to the pentaerythritol cyclic diphosphates of the present invention Invention, such as the compound E,

The acid number of the compound is inversely proportional to the hydrolytic stability of the compound, i.e. depending the greater the acid number of a compound, the lower the hydrolytic stability of the compound.

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Example 10

The thermal stability of compounds A, B, C, D and E and of 3,9-bis (2,2- / dimethy] J7-3-chloropropoxy) -2,4 »8,10-, tetraoxa-3,9 -diphosphaspiro / 5 · 57 ~ undecane-3 »9-dioxide (prepared as in Example 5 and hereinafter referred to as compound (V /), 3,9-bis (2,2 ^ ibromomethyl7-3-bronipropoxy) -2,4 , -8,10-tetraoxa-3 _y 9-diphosphaspiro / 5.5 / -undecane-3,9-dioxide (prepared as in Example 6 and hereinafter referred to as compound ((H) and 3,9-bis (2,2- ^ Chloromethyl7-3-chloropropoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5 »57-undecane-3,9-dioxide (prepared as in Eelapiel J and hereinafter referred to as compound rHj) was after in section 9-951 "Thermogravimetry Analyzer" of "Instruction Manual 990, Thermal Analyzer and Modules", E ₀ I. De Pont De Nemours and Co. (Inc.), Instrument Products Division, Wilmington, Delaware 19898. The results of the Therraogravimetric analyzes (TG-A) of the eight compounds with the various weight losses are shown in the following Table III indicated:

Table III

TG-A results ο ~

Temperature at which the weight change occurs Compound ABCDEI ¹ GH

Initial weight s-

loss 45 100 70 100 241 270 180 240

5 $ weight loss 130 172 145 180 258 302 290 317 $ 10 Wt loss 158 203-218 204 286 305 313 338 $ 25 Wt loss 225 242 250 224 310 307 335 370 $ 50 Gewo loss 347 300 278 260 331 344 355 390

-23-

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Table III clearly shows that Compounds E, F, G and H have unexpectedly high thermal stability in comparison to the compounds according to the prior art.

The superior thermal and hydrolytic stability of the compounds within the scope of this invention has significant economic implications. The superior hydrolytic stability of the compounds within the scope of those given above narrow subset allows the compounds to be superior fire retardants when they are over a aqueous system because the aqueous. "~ ^" The surrounding environment does not cause the links to migrate as easily as the Wahl et al. is the case} for the same reasons, the connections within the narrow subgroup are equally superior fire retardants if they are incorporated into objects, if the use of these objects involves exposing them against moisture.

The superior thermal stability of the compounds in the subgroup given above enables the compounds to be processed without significant weight loss at temperatures at which the closely related compounds of choice show, inter alia, significant weight losses, so that these compounds according to the prior art are not in the technical scope can be used. For example, v / ith polypropylene typically at 204 ⁰ C

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manufactured and deformed ^{at 232 0 O.} Because compounds A, B, C and D lose at least 10 ° of their weight prior to the deformation temperature of polypropylene, these materials cannot be used effectively as fire retardants for polypropylene. In contrast, Compounds E and G have excellent thermal stability and accordingly are effective fire retardants for polypropylene, as shown in Example 11 below,

Example 11

Compound the fire retardant and Pro-fax 6823 polypropylene resin in a CWo Brabender Prep Center which is equipped with a high shear compound mixer. (Profax 6823 is a trademark of Hercules Incorporated, 910 Market Street, Wilmington, Delaware 19899). The fire retardant additive is mixed dry with the polypropylene. Since the capacity of the mixer is only 300 g, a dipping process is used for mixing, which consists in flowing 300 g of the dry mixture and the remainder of add about 200 g of the flowed mixture and then use it to make another dry mixture added until the completely dry mixture is compounded. Each batch was made under the same conditions compounded, namely a temperature of 204 ° C at 120 rpm with a compounding time of 2 to 3 minutes.

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Each fire retardant system was then brought to the desired level by dry blending the ground Concentrate with the base resin. Then the base resin and fire retardant systems were melt extruded under Using a Newbury 30 Τοη Injection Molding machine. The injection molding conditions are given below, to which all systems were subjected:

. * Zbne __'_ ' .1 .... 21O ⁰ C

Prontzone 226 ⁰ C

Nozzle 15 ° C

Injection time 4-5 seconds

Cycle time 60 seconds

Deformation

temperature ~ 30 C

Flow deformation **

time 1-2 seconds

■ »O *

The resins prepared above were subjected to various tests and those derived from these tests The results obtained are recorded in Table IV below.

Table IV ^

Investigation of the fire retardancy in Pro-fax 6823 P oly-

propylene (2) O.I. (D Ul-94 Fire retardant Content fire retardant middle Means f> 17.0 HB no ——— 25.5 V-O Ξ 12.5 23.5 V-O E. 15.0 26.5 V-O G 9.0 27.5 V-O G 12.5 24.0 V-O G 16.0

\ 'UL-94 Flammability Test with a sample thickness of 1/8

inch (approx. 3.1 mm) Underwriters' Laboratories, Ine (2) Oxygen Index, ASTM D-2863-70. '-26-

7098 13/1022

The difference in terms of thermal stability is not obvious, and it consists in the difference between a material which is used more effectively as clearly shown by Example 11 given above, and a material which cannot be effectively used because of its low thermal stability during deformation and other processing methods that make it necessary exposing the material to elevated temperatures.

It should be pointed out that many modifications and changes can be made in advance without relying on the r3rfii · - dungsgede.n'rcen to deviate.

Patent claims:

709813/102 2

Claims (1)

50127a Patent claims: 1. Compound of the general formula X JEf 0 t / ° - Y-P _ 0 ——— CH CH —— 0 wherein the radicals X and X .., independently of one another, are acidic substance or sulfur atoms and the radicals Y and Y ^, independently from each other CH ₀ Z. R ι ²¹ / -0-CH ₀ -C-CH ₀ Z ₀ or -N 2 ₍ 2 2 are, in which the radicals Z .. and Z ₂ , independently of one another, fluorine, chlorine, bromine, iodine and / or hydrogen atoms and Z, fluorine, chlorine, bromine and / or iodine atoms, and in which the R and R- are, independently of one another, aliphatic, halogenated aliphatic, aromatic, or halogenated aromatic hydrocarbon groups containing no more than about 12 carbon atoms, the halogenated groups having up to about 6 halogen substituents per group. 2. Compound according to claim 1, characterized that both radicals X and X., are oxygen atoms. 709813/1022 3. Compound according to claim. 1, characterized in that both Eeste Γ and Y ₁ are, wherein Z ₁ , Z ₂ and Z ^, independently of one another, are fluorine, chlorine, bromine and / or iodine. 4. A compound according to claim 3 »characterized in that the radicals Z ₁ , Z ₂ and Z ^, independently of one another, are chlorine and / or bromine. 5. Compound according to claim 1, characterized in that that the compound 3,9-bis- (2,2- / sibromomethyl7-3-chloropropoxy) -2,4,8,10-tetraoxa-3, Q-diphosphaspiro ^ / j ?. 5] 7-undecane-3 »9-dioxide. δ. Compound according to claim 1, characterized in that the radicals Y and Y ₁ -Ν ^S 1 7. Compound according to claim 6, characterized 709813/1022 indicates that the halogen substituents on the radicals R and R _{1 are} chlorine and / or bromine. ö. Connection according to claim 6, characterized that both radicals X and X ^ oxygen are. 9. A compound according to claim 8, characterized that the radicals R and R., phenyl or halogenated phenyl or alkyl or halogenated Are alkyl groups of up to about 6 carbon atoms. 1C. Connection according to claim 8, characterized that the halogen substituents on the radicals R and R are chlorine and / or bromine atoms. 11. A compound according to claim 8, characterized that the branches R and R- phenyl- or halogenated phenyl- or alkyl- or halogenated Alkyl groups with up to 6 carbon atoms and with 0 to about 3 halogen substituents. 12. A compound according to claim 6, characterized in that the radicals R and R _{1 are} phenyl or halogenated phenyl or alkyl or halogenated alkyl groups with up to about 6 carbon atoms « -30- 709813/1022 13 · Connection according to claim. 6, characterized in that the radicals R and R., phenyl or halogenated phenyl or alkyl or halogenated
Alkyl radicals with up to about 6 carbon atoms and with 0 to about 3 halogen substituents are « 14 · Connection according to claim 1, characterized that the compound 3 »9-bis- (Ii, N-diethylamino) - 2,4> 8,10-tetraoxa-3,9-diphosphaspiro- / 5o57-undecane-3,9-dioxide is. 15 · Compound according to claim 1, characterized in that the compound 3> 9-bis- (ΕΓ, ΙίΓ-dimethylamino) -2,4 , 8,10-t etraoxa-3,9-diphosphaspiro- / 5..57- is undecane-3,9-dioxide. 16o compound according to claim 1, characterized in that the compound 3> 9-bis- (mp-bromophenylamino) -2,4,8,10-tetraoxa-3,9-dipho sphaspiro / 5 * ._ 57-undecane-3, 9-dioxide is _o 17 · Compound according to claim 1, characterized in that both radicals Y and Y ₁ -C- J ₁ 709813/1022 are, in which the radicals Z ₁ and Z ₂ , independently of one another, are fluorine, chlorine, bromine, iodine and / or hydrogen atoms and Ta, fluorine, chlorine, bromine and / or iodine atoms. 18. A compound according to claim 17, characterized in that the compound 3,9-bis (2,2- / dibromomethylJ7-3-bromopropoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro / 5.57-undecane -3,9-dioxide is. 19. A compound according to claim 17, characterized that the compound 3,9-bis (2,2- / chloromethyl7-3-chloropropoxy) -2,4,8,10-t etraoxa-3,9-diphösphaspiro / 5.j7-undeoane-3,9-dioxide is. 20. A compound according to claim 17, characterized in that the compound 3,9-bis (2,2- ₍₍ / pimethyl7_3-chloropropoxy) - 2,4,8,10-t etraoxa-3,9-diphosphaspiro / 5.57 -undecane-3,9-dioxide. 21. A compound according to claim 17, characterized that the compound 3,9-bis (2,2- ^ dimethyl7-3-'bromopropoxy) -2,4,8,10-t etraoxa-3,9-diphosphaspiro / 5.57 ~ undecane-3,9-dioxide is. 22. Compound of Formula X X. - ^Y 1 709813/1022 wherein each of the radicals X and X-, oxygen or sulfur and each of the radicals Y and Y ₁ CH ₉ Z ₁ R -0-GH ₂ -C-OH ₂ Z ₂ or -JJ is, in which the radicals Z ₁ and Z ₂ , independently of one another, fluorine, chlorine, bromine, iodine and / or hydrogen atoms, and Ζ. * are fluorine, chlorine, bromine and / or iodine atoms, and in which the radicals R and R ₁ , independently of one another, hydrogen atoms, aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbon groups having no more than about 12 carbon atoms, the halogenated groups containing up to about 6 halogen substituents per group, with the proviso that if both radicals R and R _{1 are} hydrogen atoms and both radicals X and X _{1 are} oxygen atoms, Y must be different from Y, 709813/1022